JPH02190856A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To shorten the processing time by shortening of a desilvering stage and to facilitate processing by specifying the average silver iodide content of the silver halide in all the emulsion layers of the silver halide color photographic sensitive material in the method for processing the photosensitive material with a bleach-fix bath after a color development processing. CONSTITUTION:The average silver iodide content of the silver halide in all the emulsion layers of the color photosensitive material is specified to >=10mol% in the method for processing the color photosensitive material with the bleach- fix bath after the color development processing. At least one emulsion layer has preferably >=12mol%, further preferably >=14mol% average silver iodide content. The photosensitive material preferably contains the emulsion particles in which the silver iodobromide contg. 15 to 45mol% silver iodide exists by having the distinct phase structure and in which the silver iodide content over the entire particle exceeds 10mol% in at least >=2 layers. The shortening of the processing time by the shortening of the desilvering stage and the facilitation of the processing are attained in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing exposed silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular, relates to methods for processing exposed silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention relates to an easy and quick processing method for color photosensitive materials.

(Prior Art) -a. The basic steps of processing color photosensitive materials are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. In the next desilvering step, 1. The silver produced in the color development process is oxidized by the action of the oxidizing agent (bleaching agent), and is further converted into a soluble silver complex by the ion complexing agent (fixing agent), which is then dissolved and removed.

By going through this desilvering step, only a dye image is created on the color photosensitive material.

In addition to the above-mentioned basic steps, actual development processing includes various auxiliary steps in order to maintain the photographic and physical quality of the image or to improve the storage stability of the image. For example, a hardening bath, a stop bath, an image stabilization bath, a water washing bath, etc.

In recent years, there has been a strong demand in this industry to speed up processing, that is, to shorten and simplify the processing time, and in particular, shortening the desilvering process, which accounts for nearly half of the processing time, has become a major issue. There is.

Conventionally, as a means to simplify and speed up the desilvering process, a bleach-fix solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate in one solution, which is described in German Patent No. 866.605, has been used. It has been known. By making this desilvering process a one-bath bleach-fixing process, simplification can be achieved; Since the bleaching blade is made to coexist with salt, the bleaching blade is significantly weakened, and sufficient desilvering is extremely difficult for color photographic materials with high sensitivity and high silver content, making it unsuitable for practical use. In particular, in order to improve the sensitivity and image quality of color light-sensitive materials for photographing, the use of silver halide emulsions with higher iodine content has been promoted and is becoming essential. On the other hand, methods of adding various bleach accelerators to bleach-fixing baths or their pre-baths have been proposed as a method for increasing the bleaching strength.

Such bleach accelerators are described, for example, in U.S. Pat.
3.858 specification, British Patent No. 138842, JP-A-53-141623 and JP-A-61-20945; disulfide bonds as described in JP-A-53-95630; Compounds having; Thiazolidine derivatives as described in Japanese Patent Publication No. 539854; Isothiourea derivatives as described in Japanese Patent Publication No. 53-94927; Japanese Patent Publication No. 4585
Thiourea derivatives as described in JP-A-49-26586; thioamide compounds as described in JP-A-49-42349; JP-A-49-49
Examples include dithiocarbamate salts as described in Japanese Patent No. 2349. Among them, the ability to promote bleaching is high,
Mercaptothiadiazole described in JP-A No. 61-20945 is particularly excellent because it exists stably in a bleach-fix solution, but it is difficult to fix when bleach-fixing a photosensitive material containing a high iodine emulsion. The problem was that it got worse.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a method that facilitates desilvering of color light-sensitive materials, shortens processing time, and facilitates processing.

The second object of the present invention is to shorten the processing time of color photosensitive materials with improved desilvering properties, photographic properties, especially sensitivity and graininess, and
The purpose is to provide a method that can be easily processed.

A third object of the present invention is to provide an image forming method that can obtain high-quality images through rapid processing by combining a specific color photosensitive material and a specific processing method.

(Means for Solving the Problems) The above aspects of the present invention provide one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support. A method of processing a color photosensitive material with a bleach-fix solution after color development processing, characterized in that the average silver iodide content of silver halide in all emulsion layers of the color photosensitive material is 10 mol% or more. This was achieved through a method of processing color photosensitive materials.

In the present invention, the average silver iodide content of silver halides in all emulsion layers refers to the total iodine content (AgX) of all 4 silver halides (not including metallic silver) present in the light-sensitive material. 1)
In the present invention, the average silver iodide content must be 10 mol% or more, preferably 10.5 to 20.0 mol%, and more preferably 10.5 to 20.0 mol%. Preferably it is 11°0 to 15.0 mol%.

In the present invention, it is necessary to have at least one red-, green-, and blue-sensitive silver halide emulsion layer, but preferably two or more layers each having different sensitivities, such as a green-sensitive layer and a red-sensitive silver halide emulsion layer. More preferably, the layer consists of three layers with different sensitivities.

In the present invention, it is preferable that at least one emulsion layer has an average silver iodide content of 12 mol% or more, and 14
More preferably, it is mol% or more.

In the present invention, emulsion grains in which silver iodobromide containing 15 to 45 mol% of silver iodide exist with a clear silk-like structure and the silver iodide content in the entire grain exceeds 10 mol% are used. It is preferable to include at least two layers.

The clear silk-like structure mentioned here can be determined by the method of X-ray diffraction. An example of applying the X-ray diffraction method to silver halide grains is described in H. Hirsch, Journal of Photographic Science, Vol. 10 (1962), pages 129 onwards. If the lattice constant is determined by the halogen composition, Black's condition (2dsinθ=nλ)
A diffraction peak occurs at a diffraction angle that satisfies .

Regarding the measurement method of X-ray diffraction, see Basic Analytical Chemistry Course 24 “X
It is described in detail in books such as ``Radio Analysis'' (Kyoritsu Shuppan) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using β rays as a radiation source (tube voltage 40 kV, tube current 60 mA).

In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), time constant of II, scanning speed of the goniometer, and recording speed are appropriately selected and measurement accuracy is confirmed using a standard sample such as silicon. There is a need to.

In the present invention, a distinct silk-like structure is defined by the diffraction intensity versus diffraction angle of the (220) plane of silver halide using β rays for Cu with a diffraction angle (2θ) in the range of 38° to 42″. When a curve is obtained, at least two diffraction peaks are found, one corresponding to a high iodine layer containing 15 to 45 mol% silver iodide, and the other diffraction peak corresponding to a low iodine layer containing 8 mol% or less silver iodide. There is a diffraction maximum and one minimum between them, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer. More preferably, the diffraction intensity ratio is 115 to 3/1,
This is especially the case when the ratio is 1/3 to 3/1.

In the present invention, the emulsion consisting of silver halide grains having a distinct silk-like structure preferably has a diffraction maximum (peak) in which the minimum value of diffraction intensity between two peaks is at least two peaks.
Of these, it is preferable that the strength is 90% or less of the weaker one.

More preferably 80% or less, particularly preferably 6
It is 0% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Publishing).

It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a curve analyzer manufactured by DU Pont.

Even in the case of an emulsion in which two types of silver halide grains with different halogen compositions coexist, which do not have a distinct silk-like structure, two peaks appear in the X-ray diffraction. Although such emulsion grains may be used, emulsion grains having a clear silk-like structure are preferable as described above.Is the halogen-line emulsion an emulsion consisting of silver halide grains having a clear silk-like structure, or is it an emulsion consisting of silver halide grains having a clear silk-like structure? In order to determine whether the emulsion contains two types of silver halide grains such as
on-probe micro analyzer method)
This is possible by using .

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensity of silver and iodine irradiated from each particle.

By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion is composed of silver halide grains having a clear phase structure.

In the emulsion of the present invention, it is preferable that the iodine content among the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is preferably 50% or less, more preferably 35% or less.

Another preferred interparticle iodine distribution is one in which the logarithm of particle size and iodine content exhibit a positive correlation. In other words, the iodine content of large size particles is high and the iodine content of small size particles is low. Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is preferably 40% or more, more preferably 50% or more.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. The silver iodide content may be 15 to 45 mol%, preferably 25 to 45 mol%, more preferably 3
It is 0 to 45 mol%. The most preferred silver halide for the core portion is silver iodobromide containing 30 to 45% silver iodide.

The composition of the outermost layer is preferably a silver halide containing 8 mol% or less of silver iodide, more preferably a silver halide containing 6 mol% or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. Particularly preferred for the outermost layer is silver iodobromide or silver bromide containing 0.1 to 6 mol % of silver iodide.

The average halogen composition of the entire grain is preferably such that the silver iodide content exceeds 10 mol%, more preferably 11 to 2 mol%.
It is 0 mol%, more preferably 14 to 17 mol%.

The size of the silver halide grains of the present invention is 0.1θ to 3.0
μm, preferably 0.20 to 2.00 μm, more preferably 0.30 to 1.7+zm.

More preferably, it is 0.40 to 1.4 μm.

The average grain size of silver halide grains in the present invention is
T. H. James et al. [The Theory of the Photographic Process J]
PhotographicProcessS) 3rd edition 39
The particle size geometric mean value is well known in the art, as described in P. P., Macmillan Publishing Co., Ltd. (1966). In addition, the average size can be calculated from "Introduction to Particle Size Measurement," Washiyo Seibun (Powder Engineering Society Journal, 17!!, pp. 299-313 (1980)
It is expressed as a sphere equivalent diameter as described in 1. It can be measured, for example, by methods such as the Coulter counter method, single particle light scattering method, and laser light scattering method.

The silver halide grains of the present invention may have regular crystal shapes (normal crystal grains) such as hexahedrons, octahedrons, dodecahedrons, and dodecahedrons (also spherical, potato-like, etc.). The grains may have an irregular crystal shape such as a tabular shape, and twin grains having an aspect ratio of 1.0 to 10, particularly 1.5 to 8, are preferred.

In the case of normal crystal particles, particles having 50% or more (111,) planes are particularly preferred. Even in the case of irregular crystal forms (111
Particularly preferred are particles having 50% or more of (111) faces.
) surface ratio can be determined by the Kubelka-Munk dye adsorption method. This is because dyes are preferentially adsorbed to either the (111) plane or the (100) plane, and the association state of the dye on the (111) plane and the association state of the dye on the (100) plane are spectrally different. select. The surface ratio of the (111) plane can be determined by adding such a dye to an emulsion and carefully examining the spectra with respect to the amount of dye added.

The emulsion preferred for use in the present invention can have a wide grain size distribution, but an emulsion with a narrow grain size distribution is preferred, especially in the case of normal crystal grains, the weight or number of silver halide grains of each emulsion in terms of total 90
A monodispersed emulsion in which the grain size that accounts for % of the average grain size is within ±40%, and further within ±30%, can also be used.

The effect of the present invention can be best seen in twin grains. It is preferable to contain tabular grains having two or more parallel twin planes in a projected area of 30% or more, preferably 50% or more, more preferably 70% or more.

The emulsion consisting of silver halide grains having a distinct silk-like structure and preferably used in the present invention can be prepared by selecting and combining various methods known in the field of silver halide photographic materials. .

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting the soluble root salt and soluble halogen salt can be selected from the one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a control double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, a soluble root salt, a soluble bromine salt, and a soluble iodide salt) can also be used.

When preparing the core, silver halide solvents such as ammonia, rhodan salts, 1,000 Hls, thioethers, and amines may be selected and used. It is desirable that the emulsion has a narrow grain size distribution of core grains. In particular, the aforementioned monodisperse core emulsion is preferred, and an emulsion in which the halogen composition, particularly the iodine content, of the individual grains is more uniform at the core stage is desirable.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particle is more uniform, X'
The diffraction width of ffA diffraction is narrow, giving a sharp peak.

After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
The iodine odor can be reduced by the method of accelerating the addition rate over time as disclosed by Irie and Meiki in Japanese Patent Publication No. 48-36890, or the method of increasing the addition concentration over time as disclosed by Saito in U.S. Pat. No. 4,242.445. Uniform silver iodobromide can also be obtained by the method of growing silver iodobromide grains.

These methods give particularly favorable results. Irie et al.'s method involves the production of poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid. , adding at a rate Q that is above a certain temperature acceleration and below an addition rate proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, at Q=r or above and below Q-αt:+βt+y. It is something to do.

On the other hand, Saito's method is a silver halide crystal manufacturing method in which two or more inorganic salt aqueous solutions are simultaneously added in the presence of a protective colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. In preparing silver halide grains having a clear silk-like structure according to the present invention, shelling may be carried out directly after the formation of core grains, but the core emulsion may be added to a shell for desalting. It is preferable to attach the shell after washing with water.

Shell formation can also be separately prepared by various methods known in the field of silver halide photographic light-sensitive materials, but a simultaneous mixing method is preferable. This is preferred as a method.

In the case of fine-grain emulsions, conventional tools are useful for preparing grains with a well-defined silk-like structure, but they alone are not sufficient to improve the degree of perfection of the silk-like structure. First, it is necessary to carefully determine the halogen composition of the high iodine layer. Silver iodide and silver bromide each have different thermodynamically stable crystal structures, and it is known that they do not form mixed crystals at any composition ratio. The mixed crystal composition ratio depends on the temperature during particle preparation, but is 15~
It is important to select the optimum one from within the range of 45 mol%. Although the stable mixed crystal composition ratio depends on the atmosphere, 30
It is estimated that it exists in ~45 mol%.

The temperature when growing the low iodine layer outside the high iodine layer,
Of course, it is important to select pi, p, Ag, stirring conditions, etc., but it is also important to select the amount of protective colloid when growing the low iodine layer, spectral sensitizing dye, antifogging agent, and stabilizer. It is preferable to take measures such as growing a low iodine layer in the presence of a compound that adsorbs on the surface of silver halide. It is also effective to add fine grain silver halide instead of adding water-soluble silver salt and water-soluble alkali metal halide when growing a low iodine layer.

As mentioned above, in the present invention, silver halide grains having a clear layered structure mean that there are two different halogen compositions within the grains.
It has been explained that there are essentially three or more regions, and the center side of the particle is the core part, and the surface side is the shell part.

Substantially, the two are the core part and the third region (other than the shell part).
For example, this means that there may be a layer between the central core portion and the outermost shell portion.

However, even if such a third region exists, when an X-ray diffraction pattern is obtained as described above, two peaks (two peaks corresponding to a high iodine portion and a low iodine portion) are obtained.
This means that it may exist within a range that does not substantially affect the shape of the .

That is, there is a core region with high iodine content, a middle region, and a shell region with low iodine content, and the X-ray diffraction pattern has two peaks and two peaks.
There is one minimum part between the two peaks, and the diffraction intensity corresponding to the high iodine part is 1710 ~
3/1, preferably 115 to 3/1, especially l/3 to 3/1
1, and the minimum portion is less than 90%, preferably less than 80%, especially less than 70% of the smaller of the two peaks, then such silver halide grains have substantially two distinct layered structures. They are particles with a structure.

The same applies when the third region exists inside the core portion.

The color light-sensitive material of the present invention preferably has at least two emulsion layers containing the silver halide grains of the present invention, and in the emulsion layer, the grains of the present invention are present in the cough layer. It is present in an amount of preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more of the sum of the projected areas of all silver halide grains.

Dyes used when growing the low iodine layer include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nuclei, benzindolenine nuclei, indo-/disindo-nuclei , benzoxadol core, naphthooxazole core, benzothiazole core, naphthothiazole core, benzoselenazole core, penzimiguzole core, quinoline core, etc. can be applied. These atoms may be substituted on the genus atom.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbyl nucleus can be applied.

For example, Re5search Disclosure+
Item 17643, page 23, section ■ (December 1978
It is possible to use the compounds described in 1997) or the compounds described in the cited literature.

Typical examples include the compounds described in Japanese Patent Application No. 62-47225.

Antifoggants and stabilizers are also useful compounds when growing low iodine layers. Re5search D described above
It is possible to select and use the compounds shown in the isclosure. However, there are some compounds, such as the tetrazaindene compounds shown in Examples, that do not exhibit desirable effects. Preference is given to the invention to add mercapto compounds.

The mercapto compound preferably used in the present invention is a compound represented by the general formula (n) described below.

The emulsion of the present invention may be further bonded with silver halide having a different composition by epitaxial bonding, or may be bonded with a compound other than silver halide, such as rotane silver or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Level 17.
643 and 18716, and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

1 Chemical sensitizer 2 Sensitivity increasing agent Page 23 Page 648 Right column Same as above Brightener Page 24 Dye image stabilizer Hardener Binder Plasticizer, lubricant Page 25 Page 26 Page 26 Page 27 Page 651 Left column Same as above Page 650 Right Column inhibitor The total amount of coated silver (including metallic silver) in the photosensitive material of the present invention is preferably 3.0 to 8.0 g/po, and 4.0 to 7.5 g/po.
g/rrf is more preferable, 4.5-7゜0 g/rt
More preferred is T. If the amount of silver is greater than this, there will be problems with desilvering properties and radiation resistance, and if it is less than this, the graininess will deteriorate.

The film thickness of the photosensitive material of the present invention is preferably 13 to 25 μm, more preferably 15 to 23 μm, and 17 to 22 μm.
is even more preferable. If it is thicker than this, the desilvering performance will be poor, and if it is thinner, there will be problems such as insufficient color density and weak film strength.

Next, the compound of general formula (II) will be explained.

General formula (II) Q-3M' where Q is a heterocyclic residue directly or indirectly bonded to at least one member selected from the group consisting of -3(hM"-COOM" -OH and -NR'R") , M
l and Ml independently represent a hydrogen atom, an alkali metal, a quaternary ammonium, a quaternary phosphonium, and R1, R1
represents a hydrogen atom or a substituted or unsubstituted alkyl group.

It is thought that the compound of the general formula [■] is imparted with water solubility or has improved water solubility in the pH atmosphere of the developer and flows out from the photosensitive material into the developer. In other words, if the compound of general formula (I[) is contained in a light-sensitive material, it will dissolve in the developer and contaminate the developer.

Despite this, it is truly surprising that the change in development finish characteristics is small and the fog is low. Such an unexpected effect is thought to be due to the fact that the effect of the compound of formula (II) is significantly different when it is contained in a photosensitive material and when it flows out into a developer. However, the details are unknown, and future research will clarify its behavior.

Japanese Patent Publication No. 58-9939 discloses -3OIH and -COOH as photosensitive materials containing compounds of general formula (U) which are preferably used in the present invention.

OH, NH! A silver halide color photosensitive material containing a heterocyclic mercapto compound having at least one group selected from However, there is no mention of whether the above-mentioned problems can be solved.

Specific examples of the heterocyclic residue represented by Q in the general formula [■] include an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an o:tosadiazole ring, a bentazole ring, and a pyrimidine ring. rings, thiasia rings, triazine rings, thiadiazine rings, etc., or rings fused with other carbocycles or heterocycles, such as benzothiazole rings, benzotriazole rings, benzimidazole rings, penzoxadur rings, benzoselenazole rings, naphtho rings, etc. Examples include an oxazole ring, a triazaindolizine ring, a diazaindolizine ring, and a tetraazaindolizine ring.

Among the mercapto heterocyclic compounds represented by the general formula CI+), particularly preferred are -i formula <m> and (■
) can be mentioned.

General formula (III) (L'), l-R' General formula (IV) -i In formula (m), Y and Z are independently a nitrogen atom or CR'(R' is a hydrogen atom, substituted or unsubstituted represents an alkyl group or a substituted or unsubstituted aryl group), and R3 is ~S○ffM"-COO
An organic residue substituted with at least one type selected from the group consisting of M" -OH and -NR'R", specifically an alkyl group having 1 to 20 carbon atoms (for example, a methyl group,
ethyl group, propyl group, hexyl group, dodecyl group, octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), and L' is -S
-~O--N--CO--SO- and -SO! - represents a linking group selected from the group consisting of -, where n is 0 or 1.

In addition to these alkyl groups and aryl groups, halogen atoms (F, CI, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), oryloxy groups (
phenoxy group, etc.), alkyl group (when R2 is an aryl group), aryl group (when R'' is an alkyl group), amide group (acetamido group, benzoylamino group, etc.), carbamoyl group (unsubstituted carbamoyl group, phenylcarbamoyl group) sulfonamide group (methanesulfonamide group, phenylsulfonamide group, etc.), sulfonamide group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.), cyan group,
Alkoxycarbonyl group (methoxycarbonyl group, etc.)
, an aryloxycarbonyl group (such as a phenoxycarbonyl group), and may be substituted by other substituents such as a nitro group.

Here, when there are two or more substituents -305M, -COOM''-OH and -NR'R'' of R3, they may be the same or different.

Mt means the same as that represented by general formula (II).

Next, in the general formula (IT), X represents a sulfur atom, an oxygen atom, or -N-, and R5 represents a hydrogen atom, an S-substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

L!は-CONR＆-NR'GO-8ChNR”
-NR"SO! 0CO--COO--3-
-NR'--CO- -3O--0COO--NR'C0NR'--NR'C
OO--0CONR'- or -NR'5O2NR'~
represents Rh, R? each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group.
represents a group.

R3 and Mt mean the same as those represented by the general formulas ([1) and (I[[), and n represents O or 1.

Further, as substituents for the alkyl group and aryl group represented by R4, R5, R6 and R7, the same substituents as those listed for R3 can be mentioned.

In general formula 1, R3 is 1305M" and -COO
M” is particularly preferred.

Specific examples of preferred compounds represented by general formula (II) used in the present invention are shown below.

■ 0OH CIIiCHzCIIzSOJa 0OH α's CH, CH20H.

0OH 3Oko Na C) IzCIlzSOiNa CLCOOI( C1l.

The compound represented by H3 oon -C formula (I+) is known and can be synthesized by the method described in the following literature.

U.S. Patent No. 2.585,388, 2.541°92
No. 4, Special Publication No. 42-21,842, Japanese Patent Publication No. 53-50
．． No. 169, British Patent No. 1.275.701, D. A. Berginis et al., "Journal of Heterocyclic Chemistry" (D. A. Berge
set, al,,”Journal of Heter
cyclic Che+aistry'') No. 1518
No. 1 (1978), “The Chemistry of Heterocyclic Chemistry” Imidazole and Derivatives, Part I
Try of Heterocyclic C
hemistryImidazole and Der
tives part I), pp. 336-9, Chemical Abstracts (Che+5ical Ab
struct), ■, No. 7921 (1963), 39
Page 4, E.

Hoggarth, 'Journal of the Chemical Society'
Chemical 5ociety") pp. 1160-7 (1949), and S. R. Saladra, W. Kawa,
'Organifuku Funk Shifunal Group Prevaluation', Academic Press (S, R, 5a
udler, W. Karo, “Organic Fanc.
tional Group Preparation”
AcadeIw: c Press) pp. 312-5, (
1968) M, Chamdon, et al.
,, ), Pourtin de U Société Chimique de
France (Bulletin de Ia 5ocie)
te Chimique de France), 72
3 (1954), D.A., Shirley, D.W., Alley, Journal of the American Chemical Society (D.
A, 5hirley, D, W, AIIey, J, A
mer, Chem, Soc,).

79.4922 (1954) A, Hall, W, Marchwald, Berichte (A, Wo
hl, W,? Iarchwald, Bar, ) (German Chemistry), Journal of the American Chemical Society (J, Amer, Cheta, Soc,
), 4, pp. 1502-10, US Patent No. 3.017.270, British Patent No. 940.
No. 169, Japanese Patent Publication No. 8,334, 1983, Japanese Patent Publication No. 55-5
No. 9,463, Advanced in Heterocyclic Chemistry
ic Chemistry), degree, 165-209
(1968) West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds Imidazole and Derivatives (τhe
Chemistry of 1reterocycle
ic compounds fidazole and
Derivatives), νol 1.384L Organic Synthesis (Org, 5ynth,) T
V.

Ber, 9.465 (1976
), Journal of the American Chemical Society (J, ^o+er, chen+, soc,), 4
5-12390 Japanese Patent Publication No. 50-89.034, 53-
No. 28426, No. 55-21,007, Special Publication No. 402
No. 8.496.

-IG The compound represented by formula (II) is contained in the silver halide emulsion layer and the hydrophilic colloid layer (intermediate layer, surface protection layer, yellow filter layer, antihalation layer, etc.).

It is preferable to contain it in a silver halide emulsion layer or a layer adjacent thereto.

In addition, the amount added is lXl0-'~IX10-''
mol/n? and preferably 5X10-' to IX1
0-'mol/g, more preferably 1 x 10-b~3
X 10-'mol/rtr.

By using the emulsion of the present invention, the desilvering property is not improved even if the following bleach-fixing process is performed, and the emulsion has excellent photographic properties, especially graininess.

Next, the bleach-fix solution of the present invention will be explained.

In the present invention, all known bleaching agents can be used in the bleach-fix solution, but aminopolycarboxylic acid ferric complex salts are particularly preferred. Representative examples of the aminopolycarboxylic acids of the ferric aminopolycarboxylic acid complex salts include: A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 1,3-Diaminopropanetetraacetic acid A-41,2-
Diaminopropanetetraacetic acid A-5 ethylenediamine-N-
(β-oxyethyl)-N,N',N'-triacetic acid A-6 Nitrilotriacetic acid A-7 Cyclohexanediaminetetraacetic acid A-8 Iminodiacetic acid A-9 Dihydroxyethylglycine A-10 Ethyl etherdiaminetetraacetic acid A- Examples include 11 glycol ether diamine tetraacetic acid A-12 ethylene diamine tetrapropion tetraacetic acid, but are not limited to these exemplified compounds. Among these compounds, 8-1 to A-3
, A-10 are preferred. Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts or in the form of ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. A ferric ion complex salt may be formed in a solution using diiron or the like and an aminopolycarboxylic acid.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred from the viewpoint of solubility. When used in the form of a complex salt, one type of complex salt or a complex salt of 2Jf1 or more may be used. On the other hand, when forming a ferric ion complex salt in a solution using a ferric complex salt and an aminopolycarboxylic acid, one or more kinds of ferric complex salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used.

In either case, it is preferable to use the aminopolycarboxylic acid in excess of the amount required to form the ferric ion complex salt, and it is preferable to use the aminopolycarboxylic acid in an excess of 1 to 15% of the ferric complex salt of the aminopolycarboxylic acid.

In addition, the bleach-fix solution containing the above-mentioned ferric ion complex contains
Metal ion complex salts other than iron such as cobalt and copper may also be contained.

In the present invention, the amount of bleach used per bleach-fix solution 11 is 0.05 to 0.5 mol, preferably 0.1 to 0.5 mol.
It is 0.4 mol.

Examples of fixing agents include thiosulfates (e.g., sodium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate), thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate), thioether compounds, thioureas, Although a large amount of iodide salts and the like can be used, thiosulfate is generally used, and ammonium thiosulfate is particularly preferred from the viewpoint of solubility and fixing speed, and it may also be used in combination with other fixing agents.

The amount of these fixing agents ranges from 0.3 to 12 per 12 bleach-fixing solutions.
The amount is 3 moles, preferably 0.5 to 2 moles.

Furthermore, bleach accelerators can be added to the bleach-fix bath or its pre-bath. Such bleach accelerators include, for example:
U.S. Patent No. 3,893,858, West German Patent No. 1,29
No. 0,812, British Patent No. 138842, JP-A-53
-9563'O, a compound having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (July 1978); JP-A-1988-1
thiazolidine derivatives described in US Pat. No. 3,706,561; iodides described in JP-A-58-16235; West German Patent No. 2.
Polyethylene oxide compounds described in Japanese Patent Publication No. 748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836, etc. can be used. In particular, the following general formula (I
) or a salt thereof is preferred because it has a high bleaching accelerating ability, exists stably in a bleach-fixing solution, and continuously exhibits its bleaching accelerating ability.

General formula (r) In the formula, R1 and Rz represent a hydrogen atom, a hydroxyl group, an amino group (e.g., amino, dimethylamino, diethylamine, methylamino, etc.), a carboxyl group, a sulfo group, or an alkyl group, and R3 and R4 represent hydrogen It represents an atom, an alkyl group, or an acyl group, and R5 and R4 may be connected to form a ring. M represents a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.) or an ammonium group, and n represents an integer from 2 to 5, preferably 2 or 3.

The alkyl groups represented by R1, R1, R1 and R4 preferably have 1 to 5 carbon atoms in the alkyl group portion (eg, methyl, ethyl, propyl, etc.) and may have a substituent. Substituents include carboxyl group, hydroxyl group,
Sulfo group, amino group (e.g., amino, dimethylamino, etc.), alkoxy group (e.g., methoxy, ethoxy, etc.), sulfonyl group (e.g., methanesulfonyl, methanesulfonyl, etc.), carbamoyl group (e.g., carbamoyl, methylcarbamoyl, etc.) , sulfamoyl group (sulfamoyl, methylsulfamoyl, etc.), amide group (e.g., acetylamino group, etc.), sulfonamide group (e.g., methanesulfonylamino, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), cyano groups or halogen atoms (eg, chlorine, bromine, etc.).

The acyl group represented by R3 and R4 preferably has 3 or less carbon atoms (for example, acetyl). The ring formed by connecting Rz and R1 includes a virole ring, a pyrrolidine ring, a pyrazole ring, and an imidazole ring. ring, triazole ring, morpholine ring, piperidine ring, pyridine ring, pyrimidine ring, pyrazine ring and the like.

-II In the compound (I), preferably used in the present invention, n is 1 or 2, and R3 or R
4 is a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, or a compound in which R3 and R4 are linked to form an imidazole ring, a triazole ring, or a pyridine ring.

Specific examples of the compound represented by general formula (1) are shown below,
It is not limited to these.

H3 CHiCOOH The compound represented by the general formula (1) used in the present invention is
Advanced in Heterocyclic Chemistry
icChemistry+ 9.165~209 (1
968), 2,5-dimercapto-1,3
, 4thiadiazole can be easily synthesized by alkylation. A specific synthesis example is given in JP-A No. 61-209.
It is described in Publication No. 45.

The compound represented by general formula (1), which is the bleach accelerator used in the present invention, may be contained only in the bleach-fixing bath or its pre-bath, or may be contained in the bleach-fixing bath and its pre-bath. It may also be included in the other side.

The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. per mol of lXl0-' to 1 mol, preferably lXl0-' to IXlO-
'It's a mole.

The bleach-fix solution of the present invention contains preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, bisulfites of aldehyde compounds (e.g., acetaldehyde sodium bisulfite, etc.), or carbonyl heavy sodium 6N
Acid adducts and sulfinic acid compounds are preferred; aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid) are used in the fixer to improve the stability of the fixer. and NNN'
, N'-ethylenediaminetetraphosphonic acid).

The bleach-fix solutions of the present invention include rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.) and chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and nitrates (e.g. , ammonium nitrate, sodium nitrate, etc.), pH buffers such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, ammonium sulfate Metal corrosion inhibitors such as various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone,
Known additives such as methanol can be added.

p) of the bleach-fix solution is 4.0 to 9.0, preferably
5.0 to 8.0, more preferably 6.0 to 7.5.

Further, the temperature of the bleach-fix solution can be processed at 10 to 60°C, but preferably 30 to 50°C, more preferably,
The temperature is 35-45°C.

The replenishment amount of the bleach-fixing solution is preferably 100 to 3000, more preferably 111 (per unit) of the photosensitive material.
It is 300-1000-.

Examples of the desilvering step in the present invention include, but are not limited to, the following.

Il & 11 Bleach-bleach fixing 2. Bleaching - Bleach-fixing and fixing 1IkL3 Fixing - bleach fixing Floor 4 Bleach fixing As the desilvering step, the above-mentioned step 4 is most preferable.

It is preferable that the stirring of each treatment liquid in the desilvering step of the present invention be as strong as possible from the viewpoint of shortening the desilvering treatment time. Examples of stirring means include methods described in JP-A-62-183460 and JP-A No. 62-183461. In the case of a means of colliding jets, the time until the collision is such that the photosensitive material is absorbed into the processing solution. Preferably, this is done within 15 seconds after introduction.

In the present invention, the crossover time (time in the air from when the photosensitive material leaves the processing solution to when it enters the next processing solution) is 10
It is preferably within seconds, more preferably within 5 seconds.

In addition, the desilvering process is usually performed after the development process, but
A bath for washing with water, rinsing, bleaching acceleration, etc. may be provided between these.

Furthermore, the bleach-fixing process or each step of bleaching and fixing may be carried out in a forward current or countercurrent multi-stage process.

A bleaching bath can be provided between the color developing bath and the bleach-fixing bath of the present invention. For the bleaching solution used in the bleaching bath, the bleaching agents that can be used in the bleach-fixing solution of the present invention can be similarly used. Further, as for bleach accelerators and other additives, all compounds that can be used in bleach-fix solutions can be used in the same manner.

A fixing bath can be provided before or after the bleach-fixing bath of the present invention. In the fixing solution used in the fixing bath, fixing agents and preservatives that can be used in the bleach-fixing solution of the present invention can be used, as well as fixing agents and preservatives that are known to be used in fixing solutions such as fixing accelerators. Additives can be added.

The color developing solution of the present invention will be explained below.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D~64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamido)ethyl)-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-nodoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. Preferably about 0.1 g to about 20 g,
More preferably a concentration of about 0.5g to Log.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

The preferable addition amount is 0.5 g to 1.0 g per 11 color developing solutions.
0g, more preferably 1g to 5g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 No. 0 and No. 61203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
Various I! described in No. 0616! It is preferable to add
In addition, in combination with the above compounds, patent application No. 147823/1986
No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789,
and monoamines described in No. 61-168159, etc.
Diamines described in No. 61-173595, No. 61-164515, No. 61-186560, etc., No. 61-186560, etc.
165621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, 61-186561, and 61-197419
It is preferable to use the alcohols described in No. 61-198987, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above p), it is preferable to use various buffering agents.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/l.
It is preferable that it is more than t, especially 0. 1 mol/l-
Particularly preferred is 0.4 mol/1.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferable, such as aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347,
Special Publication No. 66-39359 and West German Patent No. 2,227,
Organic phosphonic acids described in No. 639, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112
No. 7, No. 55-126241 and No. 55-65950
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1 rimethylenephosphonic acid, ethylenediamine-N, NN',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diamino Propane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4
Tricarboxylic acid, ■-Hydroxyethylidene-11-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-NN'-diacetic acid, two or more of these chelating agents may be used in combination as necessary. good.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester the metal ions in the color developer. For example, 12
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains 2M1 or less per ρ of the developer, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2.
No. 494.903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, amine compounds described in U.S. Patent No. 2,482,546, U.S. Pat. Polyalkylene oxides shown in U.S. Pat. etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener, and the preferable fluorescent brightener is a 4゜4゛-diamino-2,2'-disulfostilbene compound. Addition amount is 0-5 g/7! Preferably 0.1g~
It is 4g/l.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The smaller the amount of replenishment, the better, but 100 to 150 ON per photosensitive material! Preferably it is 100 to 800 sd. More preferably 100
-~400-.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black and white developer used at this time is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. In addition, various commonly used additives that are generally added to black and white developers can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of ml of iodide and mercapto compounds. I can give it to you.

The processing method of the present invention comprises processing steps such as color development, bleach-fixing, and fixing as described above. Here, after the treatment step with fixing ability, processing steps such as washing with water and stabilization are generally performed, but after the bath with fixing ability, stabilization treatment is performed without substantially washing with water. It is also possible to use a simple processing method that performs the following.

The rinsing water used in the rinsing process may contain known additives as required. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E,
West.

"Water (lualiLy Cr1teria')
, Phot, Sci, and Eng.

Vol, 9+Ki 6, pages 344-359 (196
Compounds described in 5) etc. can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. can. The stabilizing liquid may optionally contain ammonium compounds, metal compounds such as Bi and A1, optical brighteners, chelating agents (for example, l-hydroxyethylidene-1,1-diphosphonic acid), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used.

Here, formalin can also be removed from the solution. In this case, reduction of environmental pollution (reduction of pollution load),
This is preferable in terms of improving the working environment.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have an Mg concentration of 5 .mu./l or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, the tlA of the processing solution due to evaporation is
wJ may occur, especially when the processing amount is small or the opening area of the processing liquid is large. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The present invention can be applied to color photosensitive materials for photography such as color negative films and color reversal films.

In addition to the silver halide emulsion used in the present invention, conventionally known silver halide emulsions can be used in combination. This silver halide photographic emulsion is, for example, published by Research Disclosure +- (RD) m17643 (1978
February), pp. 22-23, “■, Emulsion Production ((Emuls
ion preparation and types)
”, and Kaimagai 18716 (November 1979), 6
48 pages, Graphic "Physics and Chemistry of Photography", Published by Paul Montell (P, GIafkides, Chesice)
t Ph1sique PhoLographique
, Paul Montel+ 1967), Duffin, Photographic Emulsion Chemistry J, published by Focal Press (G, F
, Duffin, Photographic Emul
sionChesistry(Focal Press
, 1966) ), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V,!1.Ze
lilvan et al, Making andC
oating Photographic Emuls
ion, Focal Press, 1964).

U.S. Patent Nos. 3,574.628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce and Er+ginearing), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4.
434゜226, 4,414,310, 4,
433.048, 4,439,520 and British Patent No. 2,112.157.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned RDtk17643, ■-C-G
It is described in the patent described in .

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,326
．． No. 024, No. 4,401.752, No. 4,248.
No. 961, Special Publication No. 58-10739, British Patent No. 1,
No. 425,020, US Pat. No. 1.476.760, US Pat. No. 3,973.968, US Pat. No. 4,314.023, US Pat. Preferably.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, 4. 351. No. 897, European Patent No. 73,636, US Patent No. 3.061. ．． No. 432, No. 3,725,064, RD patient 24220 (19
June 1984), JP-A-60-33552, RD&24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4,500,630, No. 4,540,654, No. 4,556,630 No., WO (PCT) 88104
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,233, No. 4,296.200, No. 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2.895826, No. 3,772,002, No. 3.
No. 758308, No. 4,334,011, No. 4,32
No. 7.173, West German Patent Publication No. 3,329,729,
European Patent No. 121,365A, European Patent No. 249°453A, US Patent No. 3,446.622, European Patent No. 4,333,9
No. 99, No. 4,753,871, No. 4,451,55
No. 9, same 4. 427. No. 767, 4,690,8
No. 89, No. 4,254゜212, No. 4,296.19
No. 9, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are disclosed in RD No. 17643, section ■-G, U.S. Pat. No. 4,1
Preferred are those described in Japanese Patent Publication No. 63,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during campling, as described in U.S. Pat. No. 4,774,181, and U.S. Pat. No. 4,777°1.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 20.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
It is described in 4,367.282, 4,409.320, 4,576.910, British Patent 2,102,173, etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
No. 4°782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. 4.310,618, etc. DIR redox compound releasing couplers, DIR couplers releasing couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.302A
R
D magnetic 11449, 24241, JP-A-61-2012
Bleach accelerator releasing couplers described in US Pat. No. 4,553.477, etc., leuco dye releasing couplers described in JP-A-63-75747, US Pat. , 774, 181, etc., which emit a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat.
41,230, etc.

These couplers can also be impregnated into loadable latentx polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

There is also a method of using a polymer as a coupler dispersion medium, as described in Japanese Patent Publication Nos. 48-30494, 51-39835,
U.S. Pat. No. 3,619.195.

There are various descriptions in West German Patent No. 1,957,467.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO38100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Yang 17643, page 28, and Questionnaire 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The present invention will be further explained below with reference to Examples.

Example-■ (Preparation of emulsion!!I) An aqueous solution of 20 g of inert gelatin, 2.4 g of potassium bromide, and 2.05 g of potassium iodide dissolved in 800 d of distilled water was stirred at 58°C, and silver nitrate was added thereto. 150 cc of an aqueous solution in which 5.0 g of potassium bromide was dissolved was added instantaneously, excess potassium bromide was further added, and the mixture was physically aged for 20 minutes. Further, according to the method described in US Pat. No. 4,242,445, 0.2 mol/β, 0.67 mol/j! , 2 mol/l silver nitrate and potassium halide aqueous solution (potassium bromide 5
A mixture of 8 mol % of potassium iodide and 42 mol % of potassium iodide was added at a flow rate of 10 cc/min to grow 42 mol % silver iodobromide grains. The emulsion was washed with water for desalination to prepare emulsion a. The finished amount of emulsion a was 900 g. The grain size of emulsion a is 0.69 μm.

Take 200 g of Emulsion A, add 850 cc of distilled water and 30 cc of 10% potassium bromide, heat to 70°C, stir, and mix 300 cc of an aqueous solution in which 33 g of silver nitrate is dissolved and 320 cc of an aqueous solution in which 25 g of potassium bromide are dissolved for 30 minutes at the same time. 800 g of an aqueous solution containing 100 g of silver nitrate
Aqueous solution of cc and potassium bromide 75g dissolved 860
silver iodide f by simultaneously adding cc for 60 minutes
A 1.09 μm silver iodobromide emulsion with ftlo mol % was prepared. Emulsion 1 is twinned with an aspect ratio of 2.3, and its (1
11) The conversion rate was 85%. In this method, sub-Table 1-1
Emulsions A-G were prepared as listed below.

Sample 101, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below in a multilayer manner on a cellulose triacetate support produced by the production method described in JP-A-62-115035.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/d units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles.

(Sample 101) 1st layer; antihalation layer black coid silver i 0.18 gelatin 1,40 2nd layer; intermediate layer 2.5-di-t-ink decylhydroquinone 0.18EX-10
,07 EX-30,05 U-10,06 U-20,08 U-30,10 0BS-10,10 HBS-20,02 Gelatin 1.04 3rd N (first red-sensitive emulsion layer) Emulsion A Silver 0 .20 Emulsion B
Silver 0.20 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX-10 EX-15 Gelatin 4th layer (second red-light emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitive dye ■ EX-2 EX-3 EX-14 EX-10 Gelatin 5th layer (3rd red-sensitive emulsion N) Emulsion D 6.9X10-' 1.8xlO-s 3.1xlO-' 0.335 0.025 0.020 0.015 0,87 Silver 1.00 5, lX10-'1.4X10-'2.3X10-' 0.400 0, 025 0.030 0.015 1,30 Silver 1.40 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye m A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ X-6 5,4X10-5 1, 4X10 bow 2.4XIQ-' 0.007 o, os.

O,095 0,22 0,10 1,63 0,060 0,040 0,70 Daughter 0,15 Silver 0.15 3.0xlO-5 1,0X10-'3.8XLO-' 0.260 X-1 X-7 X-8 X-15 B5-1 B5-4 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ HB S -1 ) (BS-4 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion D Silver 1.00 2, lXl0 7.0X10-'2.6X10-' 0.094 0.018 0.026 0.008 0,50 Silver 1.20 Sensitizing dye V 3.5XIQ-' Sensitizing dye Vl 8.0X10-' Sensitizing dye ■
3.0XIO-'EX-130,01
S EX-110,100 EX-10,025 HBS-10,25 tl13s-20,10 Gelatin 1.54 No. 10! (
Yellow Filter Shop) Yellow colloidal silver silver o, 05EX-50
,08 HBS-10,03 Gelatin 0.95 No. 11N (
1st blue-sensitive emulsion layer) Emulsion A! I 0.08 Emulsion B Silver 0.0? Emulsion C silver 0
．． 15 Sensitizing dye ■ 3.5X10-'EX-9
0,721 X-8 B5-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion C Enhanced dye ■ U! , X-9 X-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion sensitizing dye■ 0,28 1.10 Silver 0.70 2,lX10-' 0.154 0.007 0,05 0,78 Silver 0.80 2.2X10-' 0,20 0,07 0,69 0.11 0. 17 0, 05 Gelatin 1. 00 No. 151
(Second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.54 emulsion G
O,10H-10,38
O 3-10,2 O 3-20,05 Gelatin 1.20 In addition to the above components, a surfactant was added to each layer.

(Samples 102-104> Samples 102-104 were prepared by replacing the emulsion of sample 1.01 as shown in Table 1-2.

(Samples 105 to 108) Compound 01 of general formula (It) was added to each of the 5th layer, 9th layer, and 13th layer of Samples 101 to 104 at 2×10 m
Samples 105 to 108 were prepared by adding ol/m.

Structural formula of the compound used in Example 1 EX C11゜ EX-2 H NH-L; U-U-L; 1119-130X CI+.

I EX EX H EX O1+ EX H EX EX Snake X Ha X Ca1l+5(n) X-14 H X-1 H X X-13 H H, C-C CH.

CHl Leaf H2OCC1l:1 Hz H2O-C-CH3 C11゜ U-4 Co-0-CH.

BS Tricresyl nonate B5-2 Dibutyl phthalate sensitizing dye V OJa Sensitizing dye■ Sensitizing dye■ B5-3 CH2 CH3 Sensitizing dye■ Sensitizing dye■ (CHz + aS(h- (CHz+ 3sOxNa Sensitizing dye■) C1li)1 (CHz)4 So, Na The photosensitive material prepared as above was cut into a width of 35 m/m,
Wedge exposure was performed with the exposure amount of the highest density portion being 5 CMS. Thereafter, continuous processing (running processing) was performed separately using the processing steps and processing solutions described below until the cumulative replenishment amount of the developer was twice the capacity of the mother liquor tank.

Table 1-3 Processing method steps Processing time Processing temperature Color development 3 minutes 15 seconds 38°C Bleach fixing 4 minutes 00 seconds 38°C Replenishment amount Tank capacity 45mf 5N 50m 57! Water washing +21 20 seconds 35℃ 30-stable
25 seconds 35℃ 20m drying
50 seconds 65°C Replenishment amount is 350 per width 1 m length Next, write down the composition of the processing solution.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydroxyethylitine-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl- N -β-Hydroxyethylamino)-2 Add methylaniline sulfate solution and 1) 1.4 1.5 ■ 2.4 2.8 4.5 5.5 1, of 1.0n 10.05 10.10 Unit (g) Iron ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate Aqueous solution (70%) Acetic acid (98%) Add water to pH 90° 0 5.0 12,0 IR1 〇- 〇1 (Stable solution) Mother liquor, replenisher common unit (g) 2, 〇- Formalin (37% ) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.01 pH 5,0-8,0 0,30 (Washing water) Mother liquor, replenisher Common tap water is passed through a hotbed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite JR-400>) to remove calcium. and magnesium ion concentration to 3.71 or below, and then 20 g/L of isocyanurate dichloride and 0.015 g/It of sodium sulfate were added.The pH of this solution was 6.
It is in the range of 5 to 7°5.

The desilvering property of each sample was determined by the remaining 1 of the highest concentration part of the sample at the end of the run! Compared by quantity. The amount of remaining silver is fluorescent
It was determined by line analysis. RMS value indicating granularity (48μ
The results are shown in Table 1-4 along with the diameter (value at the aperture). The smaller the value, the better.

Table 1-4 * The RMS value at the exposure amount that gives the density of (minimum density + 0.2) of sample 101 is multiplied by 1000.

As is clear from Table 1-4, the samples containing the silver halide grains of the present invention had significantly improved desilvering properties even in the bleach-fixing process, and good results were also obtained in terms of graininess. Furthermore, the sample to which the compound of -C formula (I[) was added gave better results than the sample to which it was not added.

Example 2 Samples 101, 103, and 107 prepared in Example 1 were subjected to a running treatment with a bleach-fix solution to which a bleach accelerator was added. The treatment solution was the same as in Example 1, but the bleach accelerator shown in Table 2-2 was added to the bleach-fix solution, and the treatment was carried out according to the method shown in Table 2-1.

The amount of residual silver in the maximum density area and the unexposed area after bleach-fixing was measured in the same manner as in Example 1, and the bleaching performance and fixing performance were compared.

The smaller the amount of residual silver in the highest density area and the unexposed area, the better the bleaching and fixing properties, respectively. The results are shown in Table 2-2.

Table 2-1 Treatment method Process Processing time Processing temperature Color development 2 minutes 30 seconds 40℃ Bleach fixing 1 minute 30 seconds 40℃ Refill amount tank capacity■ 45I111!5p.

50m1 51 Water washing (2120 seconds 35℃ 3 (ld 24'
Constant 20 seconds 35℃ 20m1
21 Drying 50 seconds 65°C Supplementary image is 35 Width 1 m length In Table 2-2, the light-sensitive material containing the silver halide grains of the present invention can be fixed even in a bleach-fixing process containing a bleach accelerator. Bleaching could be improved without deterioration.

Example 3 The samples prepared in Example 1 were treated in the same manner as in Example 1 using the treatment method and treatment solution shown below, and the desilvering properties were compared based on the amount of residual silver in the highest concentration area. The results are shown in Table 3-2.

Table 3- Process Processing time Color development 3 minutes 15 seconds Bleached white 1 minute OO seconds Bleach fixing 3 minutes 15 seconds ■ Processing method Processing temperature Replenishment amount 38℃　　45- 38℃　　2M 38℃ 30d tank capacity Next, the composition of the treatment liquid will be shown.

(Color developing solution) Same as Example 1 (Bleach solution) Common to mother solution and replenisher Ethylenediaminetetraacetic acid Ferrous ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator Aqueous ammonia (27%) Unit (g) 120.0 10, 0 100.0 10, 0 5X10-'mol 15, (1++f Washing with water (2) 1 minute 00 seconds 35℃ 30Il!1 Stable 40 seconds 38℃ 20-Drying
Drying 1 minute 15 seconds 55℃ Replenishment amount is 47 per 1 meter length in 351I! H (Bleach-fix solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid dibasic 6.3 Units (g) Iron ammonium dihydrate Ethylenediaminetetraacetic acid dibasic acid 50°Thorium salt Sodium sulfite Ammonium thiosulfate aqueous solution Aqueous ammonia (27%) Water In addition, pH (washing water) Same as Example 1 (Stabilizing solution) Same as Example 1 5゜12゜240゜6゜1゜7゜Table 3-2 0+d 〇- 〇1 Desilvering process is bleaching-bleaching Even in the case of fixing, samples containing the silver halide grains of the present invention have excellent desilvering properties.

(Effects of the Invention) By carrying out the present invention, highly iodinated silver halide color photographic light-sensitive materials for high sensitivity and high image quality can be rapidly bleach-fixed without deteriorating fixing. Ta.

Claims (2)

[Claims] (1) After color development processing of a silver halide color photographic light-sensitive material having one or more red-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, and blue-sensitive silver halide emulsion layers on a support, A silver halide color photographic light-sensitive material characterized in that the average silver iodide content of silver halide in all emulsion layers of the silver halide color photographic light-sensitive material is 10 mol% or more in a method of processing with a bleach-fix solution. How materials are processed. (2) The following general formula (I) is used in the bleach-fix solution or its pre-bath:
A method for processing a silver halide color photographic light-sensitive material according to claim (1), which contains at least one of the compound represented by or a salt thereof. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 represent a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a sulfo group, or an alkyl group, and R
^3 and R^4 represent a hydrogen atom, an alkyl group, or an acyl group, and R^3 and R^4 may be connected to form a ring. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents an integer from 2 to 5.